End-to-End Vector Dynamics of Nonentangled Polymers in Lamellar Block Copolymer Melts: The Role of Junction Point Motion

Abstract

By using dielectric spectroscopy, we investigate the chain dynamics of nonentangled polyisoprene (PI) under soft confinement in lamellar domains of block copolymer melts with polydimethylsiloxane (PDMS). The data show a dramatic difference in the end-to-end vector dynamics of the PI blocks as compared not only with that of the corresponding homopolymer PI chains but also with respect to previous results for the same blocks under soft confinement in cylindrical domains. Two contributions to the dielectric normal mode relaxation are detected. The data are analyzed by means of a model including contributions from internal chain modes (accounting for the fastest component) and a slow component attributed to the junction point dynamics. The contribution of the internal chain modes is modeled according to the analysis of the Rouse modes obtained from simulations of a generic bead–spring model for strongly segregated symmetric diblock copolymers. In this way it is shown that the internal chain modes of the blocks have time scales close to those expected from the homopolymer chain independently of the structural details. In contrast, the contribution attributed to the junction point dynamics depends critically on minor structural differences. We interpret these findings as a result of the presence of fast moving defects and/or grain boundaries in the lamellar structures formed by these relatively short, nonentangled diblock copolymers.